Fluorescence properties and quantum-chemical modeling of tert-butyl-substituted porphyrazines: Structural and ionization effect

Synthesis and identification of tetrakis-[5,6-bis(4-tert-butylphenyl)pyrazino] porphyrazine, tetra-(4-tert-butyl) phthalocyanine and octakis-(4-tert-butylphenyl)porphyrazine were carried out. Spectrophotometric method was used to study the spectral, acidic and fluorescence properties of the synthesized compounds. It was deter-mined that the synthesized tert-butyl-substituted porphyrazines exhibit a high sensitivity of fluorescence to the molecule ionization. To understand the features of the spectral properties the geometry optimization and an analysis of energy levels and localization of highest occupied and lowest unoccupied molecular orbitals of the studied compounds were performed on the basis of density functional theory with the BP86 functional and the def2-TZVP basis set. The effect of substituents in molecular fragments of the macrocycle on the acidic and electro-optical properties of the studied compounds is revealed. Materials with pH-tunable fluorescence were designed. (C) 2020 Elsevier B.V. All rights reserved.